An unprecedented three-component reaction of arynes, tertiary amines, and nucleophiles has been demonstrated through ammonium salt intermediates. This protocol allows access to tertiary aniline derivatives containing the piperazine motif in good-to-excellent yields. Expansively, this reaction can produce biologically important 2-(4-phenylpiperazin-1-yl)ethyl-containing molecules using arynes, 1,4-diazabicyclo(2.
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